<jats:title>Abstract</jats:title><jats:p>Acovulparine (=1<jats:italic>α</jats:italic>,6<jats:italic>β</jats:italic>,7<jats:italic>R</jats:italic>,8<jats:italic>β</jats:italic>,14<jats:italic>α</jats:italic>,16<jats:italic>β</jats:italic>)‐4‐(hydroxymethyl)‐1,6,14,16‐tetramethoxyaconit‐19‐ene‐7,8‐diol; <jats:bold>1</jats:bold>), a new norditerpene alkaloid, was isolated from the MeOH extract of the whole plants of <jats:italic>Aconitum vulparia</jats:italic> R<jats:sc>eichenb</jats:sc>., together with the known compounds lycoctonine (<jats:bold>2</jats:bold>) and delcosine (<jats:bold>3</jats:bold>). The structures were established by HR‐EI‐MS and advanced 2D‐NMR, including <jats:sup>1</jats:sup>H‐NMR, JMOD, <jats:sup>1</jats:sup>H,<jats:sup>1</jats:sup>H‐COSY, HSQC, and HMBC experiments. Acovulparine was found to contain the rare C(19)N azomethine group.